Journal of Metals, Materials and Minerals, Vol.28 No.2 pp.27-32, 2018
Self-striking red glass fabrication at low temperature using gold nanoparticles
Yotsakit RUANGTAWEEP1,2,*, Jakrapong KAEWKHAO1,3 and Narong SANGWARANTEE4,*
1Center of Excellence in Glass Technology and Materials Science (CEGM), Nakhon Pathom Rajabhat University,Nakhon Pathom, 73000, Thailand 2Science Program, Faculty of Science and Technology, Nakhon Pathom Rajabhat University, Nakhon Pathom, 73000, Thailand 3Physics Program, Faculty of Science and Technology, Nakhon Pathom Rajabhat University, Nakhon Pathom, 73000, Thailand 4Applied Physics, Faculty of Science and Technology, Suan Sunandha University, Bangkok, 10300, Thailand
*Corresponding author e-mail: [email protected]; [email protected]
Received date: Abstract 9 May 2018 Revised date: This research is intended to determine the appropriate condition for gold ruby 24 May 2018 glass production at low temperature. The effects of reducing agent (SnO2 and SeO2) Accepted date: concentrations on coloration of gold nanoparticle (AuNPs) in glass samples have 29 September 2018 been investigated. The glasses with chemical compositions of SiO2, B2O3, Al2O3, Na2O, CaO, K2O, Sb2O3, SnO2, SeO2 and AuNPs were fabricated by conventional Keywords: Gold nanoparticles melt-quench technique at 1,200C in normal atmosphere. The results found that the Reducing agent red glasses were obtained by SnO2 with concentration of 0.5 wt% and SeO2 with Red glasses concentration of 0.05 wt%. The color of glasses were confirmed by UV-visible spectrophotometer in the wavelength range 300-1100 nm and color coordinate in CIE L*a*b* system. Moreover, the color of glasses were obtained immediately when took the glass out of furnace without second heat treatment.
1. Introduction temperature and soaking time in melting process, duration and temperature of the annealing step, It is well known that the red glass from gold reducing agent types and the composition of the nanoparticles (AuNPs) is interesting in glass base glass. These factors particularly affect on the industrial production because it is the most precious presence of characteristic elements influencing the and popular among all red pigments [1-3]. The glass precipitation of the metal nanoparticles [8]. doped with gold nanoparticles is known as “gold In glass production, the red glass is not easy to ruby glass” or “cranberry glass”. The red coloration produce because of coloration control difficulties, it is caused by the optical phenomenon exhibited by need a second heat treatment known as “striking”. gold nanoparticles is surface plasmon resonance Nevertheless, the gold ruby glass can be developed (SPR) [4,5]. SPR is the collective oscillation of the to the suddenly striking red color without a second electrons of conduction electrons that are excited by heat treatment, this process is called “self-striking” the interaction of electromagnetic wave. The SPR [9]. Recently, it has been reported the red glass absorption band of this interaction is strongly preparation at high temperature for self-striking dependent on the size and shape distribution of process [10,11]. However, the fuel cost for glass nanoparticles which indicate to the optical preparation at high melting temperature is high, so absorption spectra in the UV-vis region and display glass production at low melting temperature is the desired color [6]. Its found that spherical AuNPs alternative way for saving cost. In the present work, with size distribution is between few and about 50 tin oxide (SnO2) and selenium oxide (SeO2) were nm has the maximum absorption peak locate at 520- selected as a reducing agent for self-striking process 530 nm and there are red shift with the increasing at low temperature. In glass matrix, the diffused Au+ diameters of gold nanoparticles [7]. Moreover, the can be reduced to neutral atomic state (Au0) by factors affecting controlling the size distribution is reducing agents and then the gold atoms very important for the coloration in glass such as agglomerate to form nanoclusters of appropriate
DOI: 10.14456/jmmm.2018.22 28 RUANGTAWEEP, Y., et al.
size and produce the desired color [12]. Therefore, refractometer with a refractometer fluid nD ≤1.65 the effect of SnO2 and SeO2 on glass coloration and the sodium vapor lamp as the light source (539 from AuNP in self- striking process at low melting nm). The UV-Vis-NIR Spectrophotometer (UV- temperature were investigated. 3600) used to measure optical spectra of glass sample and CIE L*a*b* color coordinate calculation. 2. Experimental the excitation and emission spectra of the samples measured by luminescence spectrometer (Cary The glass samples containing a reducing agents Spectrophotometer). with different concentration were prepared in composition of SiO2, B2O3, Al2O3, Na2O, CaO, 3. Results and discussion K2O, Sb2O3, SnO2, SeO2 and AuNPs as shown in Table 1 and 2. All the chemical compositions were 3.1 Glass samples finely powder while AuNPs was solution (diameter = 16 nm). The whole of composite were mixed in a The glass samples with different reducing agents high purity alumina crusible (each batch weighs for are illustrated in Figures 1 and 2. The undoped glass 20 g). Then the batches were melted by placing shows the purple color that was obtained from them in an electrical furnace at 1200°C for 3 h. AuNPs with diameter larger than 50 nm and the After complete melting, these melts were quenched color of the glass changed with the increase of in air by pouring between preheated stainless steel reducing agent content. The glasses with SnO2 plates. The quenched glasses were annealed at concentrations of 0.1 to 0.4 wt% and SeO2 500°C for 3 h to reduce thermal stress, and cooled concentrations of 0.01 to 0.04 wt% show purple down to room temperature. Finally, all glass color while red color was occurred from SnO2 samples were cut and polished for further concentrations at 0.5 and SeO2 concentrations at investigation. 0.05 wt%. It is important to emphasize that the red The densities (ρ) were measured by the color glasses can be obtained immediately when the Archimede’s method using xylene as immersion glass is taken out of the electrical furnace. The color fluid. The corresponding molar volume (VM) was significantly changes from the purple to red color calculated using the relation, VM= MT/ρ, where MT with increasing SnO2 and SeO2 concentration. The is the total molecular weight of the multi- results reflect that SnO2 and SeO2 have an effect on component glass. Refractive index (RI) was the coloration of the glass in which may relates with measured at room temperature using a DR-M2 the nucleation of gold nanoparticles [11].
Table 1. Chemical compositions of glass samples with different SnO2 concentration.
Concentration Glass composition (wt%) of SnO2 SiO2 Na2O CaO K2O Sb2O3 Al2O3 B2O3 AuNPs SnO2 0.0 48.92 25 6 10 0.05 2.5 7.5 0.03 - 0.1 48.82 25 6 10 0.05 2.5 7.5 0.03 0.1 0.2 48.72 25 6 10 0.05 2.5 7.5 0.03 0.2 0.3 48.62 25 6 10 0.05 2.5 7.5 0.03 0.3 0.4 48.52 25 6 10 0.05 2.5 7.5 0.03 0.4 0.5 48.42 25 6 10 0.05 2.5 7.5 0.03 0.5
Table 2. Chemical compositions of glass samples with different SeO2 concentration.
Concentration Glass composition (wt%) of SeO2 SiO2 Na2O CaO K2O Sb2O3 Al2O3 B2O3 AuNPs SeO2 0.00 48.92 25 6 10 0.05 2.5 7.5 0.03 - 0.01 48.91 25 6 10 0.05 2.5 7.5 0.03 0.01 0.02 48.90 25 6 10 0.05 2.5 7.5 0.03 0.02 0.03 48.89 25 6 10 0.05 2.5 7.5 0.03 0.03 0.04 48.88 25 6 10 0.05 2.5 7.5 0.03 0.04 0.05 48.87 25 6 10 0.05 2.5 7.5 0.03 0.05
J. Met. Mater. Miner. 28(2). 2018 Self-striking red glass fabrication at low temperature using gold nanoparticles 29
The density and the refractive index should be increased when high density component added into the glass structure. However, in this work, it is found that they are independent of SnO2 and SeO2 concentration because of the volatilization of low
melting point component.
Figure 1. The glass samples with different SnO2 concentration.
Figure 2. The glass samples with different SeO2 concentration.
3.2 Density, molar volume and refractive index Figure 3. The density and molar volume of glass The obtained value of density and molar volume samples with different SnO2 concentration. are shown in Figures 3 and 4. The density of glass samples with SnO2 concentrations from 0.0 to 0.5 wt% are within the range of 2.5682-2.5820 g/cm3 and the molar volume values are in the range of 31.3898- 31.4259 cm3/mol. While the density of glass samples with SeO2 concentrations from 0.00 to 0.05 wt% are within the range of 2.5682-2.5820 g/cm3 and the molar volume values are in the range of 31.3898- 31.4259 cm3/mol. It has been observed that there is no effect of SnO2 and SeO2 concentration on these parameters. Actually, SnO2 and SeO2 are heavier than SiO2 and the glass density should be increased with increasing of SnO2 and Figure 4. The density and molar volume of glass samples with different SeO2 concentration. SeO2 content and then affect to molar volume. From this result, the dependence of density and molar volume with SnO2 and SeO2 concentration may be come from losing ratio and also due to the volatilization of low melting point component such as Na2O and K2O when glass were melted at high temperature [13]. Moreover, the refractive index value of glass samples with SnO2 and SeO2 concentration are in the range of 1.6561-1.6568 and 1.6558-1.6565, respectively as shown in Fig 5 and 6. It has been found that there is no effect of SnO2 and SeO2 concentration on such parameters. Theoretically, the refractive index is a function of density and these results maintain this trend.
According to classical dielectric theory, the Figure 5. The refractive index of glass samples with refractive index depends on density and on different SnO2 concentration. polarizability of the atom in a given material [14].
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50 nm, exhibits the absorption peak at 520-530 nm and display a red color in glass [15,16]. This result is corresponding with published literatures.
Figure 6. The refractive index of glass samples with different SeO2 concentration.
3.3 Absorption spectra and CIE L*a*b* system
The absorption spectra of glass samples are illustrated in Figures 7 and 8. The optical absorption spectra were recorded in the range 200-1100 nm at room temperature. It has been found that the absorption peak of undoped glass has predominant peak around 555-565 nm produces purple color. The glass samples with SnO concentrations from 2 0.0 to 0.4 wt% are observed in the absorption spectra with peaks around 540-560 nm and shown Figure 7. The absorption spectra of glass samples with purple color. The absorption broad band around 530 different SnO2 concentration. nm is obtained from 0.5 wt% concentrations of SnO2 and display red color. The absorption spectra of glass samples doped with SeO2 similar to SnO2 result. Within the concentration of SeO2 from 0.00 to 0.04 wt%, a predominant broad band locate around 550-560 nm and shown purple color. The glass sample with SeO2 concentration at 0.05 wt% shows the absorption board bands around 530 nm and produce red color. The result can be explained by the acceleration of the kinetics of the formation of AuNPs by using SnO2 and SeO2 as catalyst [8].
4+ 2- 2+ Sn + 2O Sn + O2 (1) Sn2+ + 2Au+ 2Au0 + Sn4+ (2)
It implies that the Au+ ions can be reduced to Au0 atom by the addition of SnO2 and SeO2. After that, the gold atoms agglomerate to condensation nuclei for the nanoparticles with appropriate size in glass matrix. However, the absorption peak position depends on the size and shape distributions of AuNPs. We compared the absorption spectra with literatures, and found that the size distribution of spherical AuNP which is in range of a few and about Figure 8. The absorption spectra of glass samples with different SeO2 concentration.
J. Met. Mater. Miner. 28(2). 2018 Self-striking red glass fabrication at low temperature using gold nanoparticles 31
Moreover, the absorption spectra were consistent Development Institute, Nakhon Pathom Rajabhat the color coordinate in CIEL*a*b* system, as University (NPRU), Suan Sunandha Rajabhat shown in Figures 9 and 10. Therefore, glass samples University (SSRU) and Center of Excellence in with SnO2 at 0.5 wt% and SnO2 at 0.5 wt% are the Glass Technology and Materials Science (CEGM) optimize concentration for a preparation of red glass for the facilities support. at low temperature by self-striking process. References
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